Condensation of pyridine dicarboxylic acids with amino anthraquinones



4 2,925,421 j 3 The" reaction between the? alpha amino anthraquinoneI.;.:CONDENSATION OF PYRIDINE .DICARBOXYLIC and the pyridinedicarboiiylic acid chloride is preferably ACIDSWITHAM NO AN I-IR Q O E 1carried'out in an inert solvent for the reactants. The

Roy A. -Pizzarello, Mount Vernon; and Paul ,Resnick, solvent should haveaboiling point high enough to pergy -Y-5 an Alf F 'sg N l l o 'di 5 mitthe reaction to proceed. Wehav e' used various chlorof; 7 "assignors q ssal: p on w. benzenes (dichlorobenzenes-trichlorobenzenes etc.) per-York a corporatlo. ofvohlo chloroethylene, nitrobenzene' etc. I

I l v "N9 Drawi lfl i n m 5;. 9 7 i r The reaction temperature mayfrom110 C.-

. Sena! N0.l6 86,0l7 v I p i 150 v I V 1. ai s,- (C 27oz) I i 10 Thepyridinedicarboxylic acid dichlorides can be pre- 7 pared inconventional manner from thecorresponding This invention relates to thepreparationgofa new group acids, eg" y reacting lhionyl chloride withthe acid in the of compounds; i.e. the condensationproducts of a onepresence f the inellt v dmolecular proportion of a pyridine dicarboxylicacid'chloride with (b) two molecular proportions of an alpha 7 aminoanthraquinone. .7 ":"ExampleL- :ii i I We have found that a newgroup'ofcompounds having '1 :1: s 1 1 1 i I. 1 "J r verydesirable;pigmentaryproperties results from con 1 g gl ggz giggggggg g ggg mfihg gg gi densing in an inert solvent for the. reactants, (a) onemo- 1 a a lecular proportion of a pyridine dicarboxylic acid chlo- 332;g fifg gg figfif gg f l t' lb) P 9* alpha :th'ionylchlorid er insulateivtheinensa iasiookc; vI111;;lgocanthraqumone, at a, temperature notinexcess of a heldqr 48 .hbufs. tilihsureicdrr'hmet slolmiqfi ,FThe Theuse of pigments incoloring textiles is historically fia fi rgfsggfizgnzgg to ,gg f zi g fi fi y -as very old, but such use was, of littlecommercial impor- -ttance, outside of specialty applications, untilpigmented 5 waterfin-lacq'uer emulsion printing pastes wcre introduced,v =1 Y 5 in about 1938'. Since -'-.then, the use ofpi'gment' s' 'for i Pl 9im coloringtextiles has expanded considerably; and tli'epopu H Pa j iof pey: y g f L V vTO One part Of the acld dlchlorldersolut onw s *ration of color intothe spinning solution has increased; 9 of alphaalfm m n.flthed'emahd r p g n t -.Il1e temperature was ra sed to l150 C.,;.and;-held for} possess those properties most satisfactory for pigments forSumng Pro g m 1 y textile coloring; i.e. (1) rightness of shade; (2),r6sis'tance 35 h product was was d p e washings; to fading by sun, etc(3) resistance to soap" and (4) wege colorless-and thendrled overnightIn an oven at resistance to drycleaning, suchas'perchloroethylenel" m f6 f u 1 d Pyridine dicarboxylicacidi chlorides that a'reoperable" I we 1grams 0 W i o WH P? V in'the invention include the following:., (a) 2,3'p'yridine; P e m f dicarboxylic acid dichloridet'quinolinic' aciddichloridflf'g;

(b) 2,4-pyridine dicarboxylic acid dichloride (lutidinic aciddichloride); (c) 2,-5-pyridinc dicarboxylic' acid dichloride(isocinchomeronic acid dichloride); (d) 2,6- pyridine; dicarboxylic..acid. dichloride (dipicolinic acid -tlichlo riide') j;-'BA-pyridine'dicarboitylic. acid r1de f15 M (cinchomer'onic acid. dicliloride) and3,5-pyridine "a1: boxylic acid dichlori'detdinicotinic'acididichloride).If V 1 As 'an alpha amino'anthraquinonereactant,we prefer ton lal m o at t qu e s tu edya p minoga hv qu n n a es, t e lb y a nol-de iya 5tiveethe hl rc ative, e l-, 0.='de. Y o

T ech Q Q d i a e a owe l vusedh:1 :1 WPref6r to use either2-,3-pyridine dicarbox ylic jacid dichloride or 2,5-pyridinedicarboxylic acid dichloride-for n ;;cond cnsations with the alpha-aminoanthraquinone;:re- ;5

," l -r V: V :15-

- Gene y, the new gr p-'o c mpoun s an e. friepre-V sentedstructurallyas 14 5;;

ls bta nche mn undwasm istant=tollsolvents n5 po es ed qe l nt shtfastnsin c llnlos etate .09p h9 s n a d c er) r w LE-Wniple) r jr i rrotheflther parr t t e acid,dichlg i i9n prc V 7 1 lipmd'i'in: Exam? liwes h ge1?:5,' "?m$i.-(9-Q7 7; i v mole): Qt alpha: ry anth aqi inose; 4taiuiilg} the; sam e m q fland jag-21min e,

, V 3 a yield of grams of an *orange colored compound corresponding tothe structure was obtained. The compound was resistant to solventspyridine dicarboxylic acid, "55 grams of thionyl--'chloride end-250grams of ortho-dichlorobenzene at 8'5 complete solution was obtained.The excess thionyl chloride was removed and the solution of acidchloride Q .'cooled=to room temperature. To this solution was added 22grams (0.085 mole) of alpha-amino-S-chloroeanthrti- 'quinone and thereaction heated at 140'150 C. for 3 37 cc. of thionyl chloride. 7 Thecharge was heated to 100 C. and held for 48 hours to insure completesolution. Then, the temperature was raised to 160 C. and the excessthionyl chloride distilled off. The solution of acid dichloride wasthencooled to 100 C., clarified with charcoal and filter cell anddivided -into -two equal parts.

Toone part of the acid dichloride solutionwas added 22 grams(0.0785'mole) of alPha-amino-B-chloro anthraquinon'e. The temperaturewas raised to 150 C. and held for 3 hours. After cooling to '80 C., theproduct was isolated by 'drowningin methanol, filtering and washing withalcohol until the washing was colorless. A yield of 22 grams of 'agreenish yellow colored compound corresponding to the structure 5 wasobtained. The compound possessed good solvent hours. The reaction wasthen cooled to room temperature and drowned in 600 cc. of methanol.After filtration. the condensation product was washed clear withcompound"was resistant ftdmethandl no blee'd) resistance :andlightfastness in a cellulose acetate film. (200 plus hours infadeometer.)

Example 5 To the other ,part of the acid chloride solution-(prej pared.inwExample -4 was added 29 grams;(0.085:m01c;)-0falpha1amino-4-benzoyl-amino:anthraquinone. The temperature was raised to150 C. and held for} hours. After cooling 'to 80 C., thekproduct wasisolatedyby drowning in methanol, filtering andwashing with alcoholuntil the washings were colorless. A yield of 30 grams of aredcoloredcompound correspondingto thestructure obtained. 'The compound possessedexcellent solvent 0 resistance and excellent lightfastness ina celluloseacetate and to 'acetone -(no 'bleed-)fand had a minimal bleed finperchloroethylene; It possessed goocl lightfastness in a a celluloseacetate film (150 hours in the AATCC fadeometer). r f

Example 4 :A- solut'ion ofTZ-S: pyridine dicarboxylic'acid dichlorideinfortho dichloro benzene was prepared "by charging to a-5:00 -cc.,fiask 250. cc. of orthodi'chloro benzene, 20" grams mole) of 2-5pyridine: dicarboxylic acid, and

'lilm (200 plus hours in the fadeometer).

' 1 -Example=6 V H i 'To'a 500cc. flask was charged 21.4 gramsf(0.lmole) of isocinchomeronyl chloride, 250 cc. "of *ort'h'odichloro benzeneand 40' grams (0.18 mole) of alpha-amino anthraquinone. The charge washeated to 130 C. 'and held there for 3 hours. .Aftercooling to" C., theproduct was filtered and washed with methanol until the 6 washings werecolorless. Theproduct*was then dried at C. and a yield of 45 grams ofreddish yellow -'con'1- "pound in crystalline formand corresponding tothe structure a I grams-( 0.044 moteyqr e151:

'-' -i uinne. A yieldr f 7:5 grams bf'gan'orang e compound correspondingto thestructur orthod ichloro benzene, 17 grams (0.1 mole) ofisocinchomeronic acid and cc. of thionyl chloride. The charge was heatedto C. and held for ,48 hours until completely solu-- bilized. Thetemperature was then raised to C.

and the excess thionyl chloride distilled ofi. 2 grams Darco and 2 gramsof filter cell were added for clarification and the charge then filteredat 80 C.

45.5 grams (0.18 mole) of alpha-amino-4-methoxy anthraquinone was thenadded to the filtered solution and the temperature raised to 110 C. forthree hours. The resultant product was drowned in acetone,suction'filtered and washed withf acetoneiuntilf: bleed free, 7 There;rere sulted' 54 grams :ofa solve'nt resistant orange colored compoundposs essing excellent lightfastness-in cellulose acetate films 200 plushours in the fadeometer) and corresponding to the structure Example 8' tx 1 a idtd al e w r ein ate-mar "rh Canaa f structure nd wascharacterized I lightfastn'essi ima cellulosic acetate filr'n (200 plushours in thefadeometer) and was solvent resistant.

Example 10 dicarboxylic aciddichloride in 7 grams of.ortho-dichloro-benzene was. added l9l.5 grams (0.077 mole) of.alpha-amino-4-methoxy anth'raquinone, The reaction was heated for 3hours at C., cooled to room temperature, and the resultant productdrowned in methanol; After filtering and washing clear with methanol, 18grams "ofvan orange colored compound. correspondingto the charged vintoa; 3 neck flask. The charge was heated to 'quinone added. Thetemperature was raised to105 C.;

heated for 3 hours at ,thau'tempera'ture, and then.;lowered 1 ,to50 C,The resultantrproductwasdrownedingacetonef isuetion filtered, and thenwashed with acetone, ;until the 'washingswere colorless. 'A..yield01250.5 gramsofayellow colored compound corresponding ;to thestructure iwasobtained. Thecompound was characterigdd good f p lightfastness inaicelluloselacetate' filmjf (200, -plus;hours the 'fadeometer) an'dwassolventresistantfi i i e-p ocedure'of 'anthraquinone' was substitut'd fo7 a '50 C. and 10 grams (0.052 mole) ,of alpha-amino antha- 1 a nd. w shqaawit z lsflhql u l-411 was n s; Til r 40 corresponding to'thestructure,- A

ob tainedtf Ih" compound ha'd eicelle nt shlvent;

sistanceandwas very lightfast in a cellulose acetate film v plus-hoursin; the AATCC fadeometer).

tE aii;

' 1,613 g am s.1' '0.o31 nine -0? 2-4 pyridine' dic arboxylic' aciddichloridefl'was reacted with 10 grams (0.0?4 5-" mole) .otfalphaaminoanthraquinone in ortho idichlorobenzene jzfat 105 C. for 3 hours; .A'ftrcooling to 80 C;,-'the product was isolated by drowning in methanol,filtering to co o A i ld ?;12 a n f -l h iicplerl d ompcun it To asolution o ii 12' grams (0.058 mole) .3,4-pyri din'e 7 aciddichlorid'e'jwas reacted, with 15. grams (0.044 mole) I "of 1alpharamino-4-benzamido anthraquinone inortho di-'vchloro-benzene;at1l05? Cffor 13 hours. fAfterz zcooling, to .1 80';jC., -the fproduct: was' -isolatedf'by drowning in r tme'thanol,filteringandlwashing' withfalcoholuntil the I structure mole). ofalpha-amino-4-benaaniido anthraquinone and washings were colorless. Ayield of 17 gramsof a .red v the reaction heated at 115 C. for 3 hours.After isolatcolored compound corresponding to the structure H v H p iii--N-- Ami-'6 l 0 o N- N-C N 0: =0

was obtained. The compound had good lightfastness in ing "the resultantcondensation productv in the convena cellulose acetate film (200 plushours in the 'fadeornti'onal manner, a yield of 31 grams of anorange-red eter) and was solvent resistant. colored compoundcorresponding to the structure Example 13 To a'solution'of 19 grams(0.093 mole) of 2-4 pyridine 2o dicarboxylic acid dichloride in 250grams of nitrobenzene was added 22 grams (0.085 mole') of alpha-aminoA-chloro-ant'hraquinone. After heating for 4'hours at 140 C., the reactionwas cooled to room temperature and the resulting product drowned in 600parts of alcohol. When filtered and washed free with alcohol, a yield of20 grams of a yellow colored compound corresponding to the ll H 80 wasobtained. The. compound was characterized by resistance tOi'SOlVBHtS andgood lightfastness in a cellulose I acetate 'filrn (200'p1us hours inthe fadeometer).

Example 16 was obtained. The compound was resistant-to solvents IToas'olution oil-2 grams (0.059 mole) of 2-6 pyridine 22s g i 2322 3221excellent hghtfasmess (200 plus dicarboxylic acid dichloride in 1 25 cc.of nitrobenzene was added 19.5 grams (0.077 mole) of alpha-amino-4-methoxy anthraquinone" and the reaction heated at 150 C. for 3 hours.After cooling to room temperature, is the condensation product wasdrowned in 600 cc. of methanol, filtered and washed clear with methanol.20

Example 14 A solution .of 2-6 pyridine dicarboxylic acid dichloride inortho dichlorobenzene was prepared by charging 24 grams (0.143 mole)of-.2-6-.pyridine dicarboxylic acid, 38 grams of thionyl chlorideand.-2'50:cc.'of ortho-dichloro benzene .into'ia 3 neck flash; Thecharge wasfheated at 100 C. overnight to effect solution and the excessthionyl V chloride distilled oil at 150 C. The solution'was then I 1 thestructure cooled to 100 C. and clarifiedwith Darco G-60 filter cell.(Darco G -60 filter cell is the trade name for an activated carbonproduced by the Darco Department of the Atlas Powder Company.)

To cnehalfof the acid dichloride solution was charged 20 grams (0.090:mole) of-alpha amino anthraquinone. After heating the reaction at 115C. for 3-11 m, the resultant product was isolated in conventional mannerand a yield of 21 grams ofa very greenish yellow 7 7 compoundcorresponding to the structure was obtained. The compoundwas resistantto solvents V and was further characterize'dby good lightfastness -in a-.cellul ose acetate .film .(200 .plus hours in the fadeometer);

Our new group or" compounds possess highly satisfactor-y p'igmentaryproperties. They fare usefulfor both pigment "printing and pigare usefulfor coloring cellulose acetate and viscose spinning solutions. Theyare'also useful for nitrocellu- WaS Obtamed- The (Impound wascharacterized by good lose lacquers for automobiles, and have sufiicientresistlightfastness in a cellulose acetate filmr(200 plus hours mm; fbutdoor Sign fi i h in the fadeorneter) and had good resistance tosolvents. Sin-cs a b i changes and difi g i be made in the details abovedescribed without departing Example 15 from the nature and spirit :ofthe invention, it is to be To the second half of the acid dichloridesolution understood that the invention-is not to be limited exceptprepared Example 14 was charged 30 grams (0.089 as settforth in theappended claims.

grams of an orange colored compound corresponding to ment'dyeing of'teiitiles with synthetic resin binders and erties and being representedstructurally as .1;

.Weclaim: 1. Compounds possessing desirable pigmentary properties andbeing represented structurally as wherein R is a member selected fromthe'group consisting of alpha amino anthraquinonyl radicals, alpha aminomethoxy anthraquinonyl radicals, alpha amino chloro anthraquinonylradicals, alpha amino benzoyl amino anthraquinonyl radicals, and alphaamino benzamido anthraquinonyl radicals. Y

2. Compounds possessing desirable pigmentary proper ties and beingrepresented structurally as V wherein R is a member selected from thegroup consist ing of alpha amino anthraquinonyl radicals, alpha aminom'ethoxy anthraquinonyl radicals, alp'ha amino chloro anthraqu-inonylradicals, alpha amino benzoyl amino,

anthraquinonyl radicals, and alphaamino benzamido l anthraguinonylradicals. g

3. A'compound possessing :des'irable pigmentary propf1) (1ENH i V I 4. Acompound possessing' desirable pigmentary 1 j,

and being represented structurally as f a i 10 SICompQunds' possessingdesirable pigmentary properties and being represented structurally asO-NH--R wherein R is a member selected from the group consisting ofalpha amino anthraquinonyl radicals, alpha amino methoxy anthraquinonylradicals, alpha amino chloro anthraquinonyl' radicals, alpha aminobenzoyl amino anthraquinonyl radicals, and alpha amino benzamidoanthraquinonyl radicals. a V

6. A compound possessing desirable pigmentary properties and beingrepresented structurally as E ii 7. A compound possessing desirablepigmentary properties and being represented structurally as all Q v Q itLI 9; The method preparing compounds possessing wherein' k .is a memberselected from the group consistv p of alphaamino anthraquinonylradicals, alpha amino methox-y anthraquinonyl anthraquinonyl radicals,

radicals, alphaamino chloro alpha amino benzoylamino anthraquinonylradicals, and alpha amino benzamido anthraquinonyl radicals, in; aninert solvent for proportion of a pyridine dicarboxylic acid dichloridewith ,i two molecular proportions of an alpha-amino anthra-' quinone atatemperature not in excess-of 150 C.'-

References Cited in the file of this patent V UNITED STATESPATENTS 7compound possessing desirable pigmentaryprop- 'erties andbeingrepresented structurally as a I which comprises condensing, thereactants, one molecular Kunzetal May 11.719311 f UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION- Patent No 2,925,421 February 16, 1960Roy A Pizzarello et a1.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column l, line 35 for "rightness" read brightness Signed and sealed this20th day of September 1960.

(SEAL) Attest:

KARL H. 'AXLINE Attesting Officer Commissioner of Patents ROBERT (J.WATSON

1. COMPOUNDS POSSESSING DESIRABLE PIGMENTARY PROPERTIES AND BEINGREPRESENTED STRUCTURALLY AS